A kind of mixing solid-liquid electrolyte lithium batteryTechnical field
The invention belongs to lithium storage battery technical field, in particular to a kind of mixing solid-liquid electrolyte lithium battery.
Background technique
In mixing solid-liquid electrolyte lithium battery, solid electrolyte is main electrolyte ingredient, and liquid electrolyte is then rightSolid electrolyte is assisted comparing with traditional liquid lithium storage battery, and mixing solid-liquid electrolyte lithium battery has energy closeThe advantages that spending height, good mechanical property, good safety.After mixing solid-liquid electrolyte, lithium storage battery can directly use metalLithium does cathode, significantly improves battery energy density, while solid electrolyte membrane can also inhibit the generation of Li dendrite, so thatThe security performance of lithium storage battery is significantly improved.
Currently, main, there are three the solid electrolytes of classification: 1. organic polyelectrolyte, 2. inorganic solid electrolyte,3. the composite electrolyte that organic polyelectrolyte and inorganic solid electrolyte are combined.
The battery easy processing of organic polyelectrolyte, can continue to use existing lithium-ion electric pool process, but its room temperatureConductivity is low.Although the room-temperature conductivity of inorganic solid electrolyte is higher, its material cost is higher, and battery process is multipleIt is miscellaneous, it needs to develop many completely new battery production equipments, cost is caused further to increase.
Relative to two class solid electrolyte of front, composite electrolyte has the workability of organic polyelectrolyte,And room-temperature conductivity can be improved to a certain extent, but its bad mechanical strength, it is easy to cause film to be easily broken and causes battery shortRoad.For this purpose, people usually will be coated with the diaphragm made of the polymer such as PP, PE between composite electrolyte and positive electrode,To guarantee the partition of positive and negative anodes in lithium storage battery, while good supporting role is provided for composite electrolyte membrane, guarantees lithium electric power storageThe safety in pond.
However, although diaphragm has good supporting role, if diaphragm is by the puncture of the foreign matters such as steel needle or hits and goes outIt now ruptures, the liquid electrolyte in lithium storage battery can fill the position of membrane ruptures, so that inside lithium storage battery justPole is mutually connected with cathode, leads to the short circuit of lithium storage battery, and thus there are some potential safety problemss for the lithium storage battery.
Summary of the invention
In view of the deficiencies of the prior art, the present invention intends to provide a kind of mixing solid-liquid electrolyte lithium electric power storagePond eliminates diaphragm in the lithium storage battery, still has good mechanical strength, guarantees its excellent electric cycle performance, have simultaneouslyThere is higher safety.The lithium storage battery realizes the one-pass molding of lithium storage battery by extruding technology, easy to operate, improves lithiumThe production efficiency of battery.
To achieve the above object, the present invention provides the following technical scheme that
A kind of mixing solid-liquid electrolyte lithium battery, including positive plate, negative electrode tab and be set between positive plate and negative electrode tabComposite solid electrolyte piece, the composite solid electrolyte piece includes solid electrolyte core layer, is set to solid electrolyteCore layer towards positive plate side the first cushion gum layer and be set to solid electrolyte core layer the towards negative electrode tab sideTwo cushion gum layers；The solid electrolyte core layer is mainly by core layer inorganic solid electrolyte, electrolytic polymer and electrolysisMatter additive mixes；First cushion gum layer and the second cushion gum layer mainly include the electrolysis of cushion gum layer inorganic solid-stateOne of matter, cushion gum layer lithium salts, cushion gum layer additive or a variety of mixtures, and the first cushion gum layer or the second bufferingThe weight of glue-line accounts for the 5%-70% of the weight of composite solid electrolyte piece.
By using above-mentioned technical proposal, in solid electrolyte core layer, core layer inorganic solid electrolyte ensure that multipleThe excellent room-temperature conductivity of solid electrolyte piece is closed, electrolytic polymer is uniformly mixed in core under the action of electrolyte additiveIn central layer inorganic solid electrolyte, and polymer itself has good mechanical strength and hot melt, can be in certain journey with thisDegree on can improve core layer inorganic solid electrolyte itself and its between the first cushion gum layer and the second cushion gum layerViscosity, while good supporting role is provided for core layer inorganic solid electrolyte, so that solid electrolyte core layer hasExcellent mechanical strength guarantees the excellent electric cycle performance of lithium storage battery with this.
In addition, since polymer usually has good insulating properties and resilience, and have in the molten state goodStickiness, therefore it is mixed the circuit partition that can be realized positive plate and negative electrode tab in core layer inorganic solid electrolyte；PhasePartition for diaphragm, the present invention in electrolytic polymer can also be used as bonding agent, it is inorganic to be preferably scattered in core layerIt is bonded between solid electrolyte and to it, so that solid electrolyte core layer has certain resilience, even if there is steel needleEqual foreign matters pierce through or hit the solid electrolyte core layer and solid electrolyte core layer is ruptured, the solid electrolyteThe gap of rupture is reduced or even is restored under the action of electrolytic polymer by core layer, so that original excellent partition be kept to imitateFruit guarantees the excellent security performance of lithium storage battery；
Cushion gum layer inorganic solid electrolyte in first cushion gum layer and the second cushion gum layer make electrolyte core layer with justThere are an ion concentration gradients between pole piece and negative electrode tab supplements a certain amount of in conjunction with buffer layer lithium salts for lithium storage batteryLithium ion improves the electric cycle performance of lithium storage battery；Cushion gum layer additive then can aid in cushion gum layer inorganic solid-state electricitySolution matter and buffer layer lithium salts are sufficiently mixed, and guarantee the excellent buffer function of cushion gum layer.
To sum up, the mechanical strength that lithium storage battery of the invention still can keep its excellent after removing diaphragm, guarantees lithiumThe normal use of battery, while the security performance and battery performance of lithium storage battery are also improved to a certain extent.
Positive plate and negative electrode tab are made of some existing materials in the present invention.The positive electrode of positive plate is preferablyLi1+zCo1-nAnO2, ternary material Li1+zNixCoyM1-x-y-nAnO2, lithium-rich manganese base material mLi2MnO3·(1-m)Li1+z-NixCoyMn1-x-y-nAnO2, nickel galaxite Li1+zNi0.5-hMn1.5-lAnO4, lithium ferric manganese phosphate Li1+zFexMn1-x-nAnPO4, manganeseSour lithium Li1+zMn2-nAnO4, LiFePO4 Li1+zFe1-nAnPO4, and it is above-mentioned after solid electrolyte cladding or physical mixedOne of positive electrode or a variety of mixtures；Wherein, 0.1,0 < x < of 0≤z < 0.1,0≤n <, 1,0 < y <, 1,0 < x+Y+n < 1,0 < m < 1, h+l=n, M are Mn or Al, at least one of A Ti, Mg, Al, Zr, Nb, Ba, La, V, W, Ag, SnElement.
The negative electrode active material of negative electrode tab is preferably carbon material, tin-based material, silica-base material, transition metal oxide, goldBelong to lithium, lithium alloy, LixC6(0 x≤1 <), the transition metal nitride type solid electrolyte containing lithium and lithium titanate sillOne or more mixtures；Wherein carbon material has graphite-like, amorphous carbons etc., tin-based material have pure tin, tin oxide,Tin alloy etc., silica-base material have the sub- silicon of nano-silicon, oxidation, Si-C composite material etc..
As a result, technical staff can basis when the present invention selects positive electrode or negative electrode material during the preparation processIt is actually required and make a choice, so that lithium storage battery obtained has more excellent performance.In addition, though the invention disclosesAbove-mentioned several positive electrodes and negative electrode material, however, it is not limited to this.
Further, the thickness ratio of first cushion gum layer, solid electrolyte core layer and the second cushion gum layer is (5-30): (40-90): (5-30).
Further, in the solid electrolyte core layer, the core layer inorganic solid electrolyte, electrolyte polymerizationObject, electrolyte additive weight ratio be (40-89): (10-50): (1-10).
Applicant obtains by lot of experiment validation, when the first cushion gum layer, solid electrolyte core layer and the second bufferingThe thickness ratio of glue-line is (5-30): (40-90): (5-30), core layer inorganic solid electrolyte, electrolytic polymer, electrolyteThe weight ratio of additive is (40-89): (10-50): when (1-10), the excellent combination property of lithium storage battery obtained is corresponded to,It can be by large-scale popularization and application.
Further, in the solid electrolyte core layer, the core layer inorganic solid electrolyte is solid for oxide typeOne of state electrolyte, sulfide type solid electrolyte and nitride type solid electrolyte or a variety of mixtures.
The oxide type solid electrolyte is Garnet-type solid electrolyte material, NASICON type solid state electrolysis materialOne of material, LISICON solid electrolyte material and Ca-Ti ore type solid electrolyte material or a variety of mixtures.
The sulfide type solid electrolyte is crystalline state or amorphous Li2S-P2S5, crystalline state Li4MS4, crystalline stateLi10NP2S12、Li2S、Li3PS4、Li3P(SxO1-x)4And the Li of crystallite state2S-P2S5One of-LiX or a variety of mixingObject；Wherein, M is selected from one of Si, Ge, Sn or a variety of, and N is selected from one of Si, Ge, Sn or a variety of, and X is selected from Cl, Br, IOne of or a variety of, 0 < x < 1.
The nitride type solid electrolyte is Li3One or two kinds of mixtures of N and LiPON.
Oxide type solid electrolyte, sulfide type solid electrolyte and nitride type solid electrolyte, compared to poly-The solid electrolyte materials such as object, compound, film are closed, chemical property is active, can quickly ionize out electronics, has excellentLithium ion conductive, so that lithium storage battery has excellent conductivity.
In disclosed oxide type solid electrolyte, Garnet-type solid electrolyte is preferred are as follows: Li7A3B2O12, wherein A beOne of La, Ca, Sr, Ba, K or a variety of, one of B Zr, Ta, Nb, Hf or a variety of；NASICON type solid electrolyteIt is preferred that are as follows: Li1+xAxB2+x(PO4)3, wherein x between 0.01-0.5, one of A Al, Y, Ga, Cr, In, Fe, Se, La orIt is a variety of, one of B Ti, Ge, Ta, Zr, Sn, Fe, V, metal hafnium Hf or a variety of；LISICON type solid electrolyte is preferred are as follows:Li14A(BO4)4, wherein A is one of Zr, Cr, Sn or a variety of, one of B Si, S, P or a variety of；Ca-Ti ore type solid-stateElectrolyte is preferred are as follows: Li3xA2/3-xBO3, wherein x is between 0.01-0.5, one of A La, Al, Mg, Fe, Ta or a variety of, BFor one of Ti, Nb, Sr, Pr or a variety of.Although the invention discloses above-mentioned several oxidized form solid electrolytes, not officeIt is limited to this.
Further, in the solid electrolyte core layer, the electrolytic polymer be PEO, polysiloxanes, PPC,One of PEC, PVC, PAN, PAA, PVDF, PVDF-HFP, PMMA, NHD, PEI or a variety of mixtures.
Polyethylene glycol oxide (PEO), polysiloxanes, poly (propylene carbonate) (PPC), polyethylencarbonate (PEC), polyvinyl chloride(PVC), polyacrylonitrile (PAN), polyacrylic acid (PAA), Kynoar (PVDF), Kynoar-hexafluoropropene (PVDF-HFP), polymethyl methacrylate (PMMA), polyethylene glycol dimethyl ether (NHD), polyetherimide (PEI) can be filled out preferablyIt fills in the particle of inorganic solid electrolyte, obtains the composite solid electrolyte piece with microcellular structure, and lithium ion is at theseMigration velocity in micropore is fast, so that the composite solid electrolyte piece room-temperature conductivity with higher.In addition, when electrolysisWhen matter polymer is preferably one of PAA, PVDF, PVDF-HFP, PMMA or a variety of mixtures, corresponds to lithium obtained and storeBattery has more excellent conductivity.
Further, in the solid electrolyte core layer, the electrolyte additive is stearic acid, stearate, stoneOne of wax, siloxanes, metallic soap, dibutyl phthalate, dioctyl phthalate, hexamethylene, sulfonate are moreThe mixture of kind.
Stearic acid, stearate, paraffin, siloxanes, metallic soap, dibutyl phthalate, dioctyl phthalate,Hexamethylene and sulfonate are that can reduce the friction between inorganic solid electrolyte and electrolytic polymer as lubricant,Convenient for the extrusion molding of solid electrolyte core layer.
Further, in first cushion gum layer and the second cushion gum layer, the cushion gum layer lithium salts, cushion gum layer addThe weight ratio for adding agent is 5-15:1-10, and the weight of cushion gum layer inorganic solid electrolyte accounts for the first cushion gum layer or the second bufferingThe 20%-60% of the weight of glue-line.
Lithium storage battery is cushion gum layer lithium salts in cushion gum layer, slow when comprehensively considering the performances such as battery performance, security performanceRush glue line additive weight ratio be 5-15:1-10, the weight of cushion gum layer inorganic solid electrolyte account for the first cushion gum layer orThe 20%-60% of the weight of second cushion gum layer corresponds to lithium storage battery obtained and is optimal.
Wherein, the cushion gum layer inorganic solid electrolyte in the present invention is mainly that lithium storage battery supplements lithium ion and makesLithium storage battery has good cycle life, therefore, material and core layer the inorganic solid-state electricity of the cushion gum layer inorganic electrolyteWhether the material for solving matter is consistent unrelated, when in use both can be identical as core layer inorganic solid electrolyte, can not also be identical.
Further, in first cushion gum layer and the second cushion gum layer, the cushion gum layer lithium salts includes LiClO4、LiAsF6、LiBF4、LiPF6、LiCF3SO3、LiTFSI、LiC(CF3SO2)3, one of LiBOB or a variety of mixtures.
Lithium perchlorate (LiClO4), hexafluoroarsenate lithium (LiAsF6), LiBF4 (LiBF4), lithium hexafluoro phosphate(LiPF6), trifluoromethyl sulfonic acid lithium (LiCF3SO3), bis- (trifluoromethane sulfonic acid) imine lithiums (LiTFSI), three (trifluoromethyl sulphursAcid) lithium methide (LiC (CF3SO2)3) and di-oxalate lithium borate (LiBOB) in be the lithium salts containing acid ion, can be quickLithium ion is ionized out, is supplemented when lithium ion deficiency in lithium storage battery, in addition the acid ion of its generation is unstable, works as lithiumLithium ion in battery is combined when extra, provides the system of a dynamic equilibrium as lithium storage battery, is improved lithium and is storedThe electric cycle performance of battery.
Further, in first cushion gum layer and the second cushion gum layer, the cushion gum layer additive is PEO, gathersOne of siloxanes, PPC, PEC, PTMC, VC, fluoromethyl carbonic ester, fluoroethyl groups carbonic ester or a variety of mixtures.
By using above-mentioned technical proposal, Pluronic F-127 (PEO), polysiloxanes, polypropylene carbonate (PPC), poly- carbonSour ethyl (PEC), polytrimethylene carbonate (PTMC), vinylene carbonate (VC), fluoromethyl carbonic ester and fluoro secondBase carbonic ester is high molecular polymer, while playing good supporting role, additionally it is possible to solid electrolyte core layerIn electrolytic polymer it is preferably compatible, to increase the bonding firmness of solid electrolyte core layer and cushion gum layer.
Further, the preparation method of the lithium storage battery includes following operating procedure:
1., the preparation of buffering adhesive
Be formulated for molding the first cushion gum layer and the second cushion gum layer buffering adhesive, specifically: by cushion gum layer additive withCushion gum layer lithium salts is dissolved in solvent, is added cushion gum layer inorganic solid electrolyte, is buffered accordingly after mixing dispersionGlue；
2., the preparation of solid electrolyte rubber master batch
Core layer inorganic solid electrolyte first is carried out being mixed and made into masterbatch with electrolytic polymer, then masterbatch and electrolyte are addedAdd agent to be added in extruder, obtains solid electrolyte rubber master batch through extruder heating and mixing；
3., co-extrusion modling
1. buffering adhesive that step is prepared and 2. solid electrolyte rubber master batch that step is prepared are injected into extruder by the structure of settingAppointed part is once squeezed out by coextrusion technology, composite solid electrolyte piece is obtained after solvent evaporated, then by positive plate and bearPole piece passes through compression molding of hot pressing lamination process, injects liquid electrolyte after solvent evaporated, final mixing solid-liquid is madeElectrolyte lithium battery.
By using above-mentioned technical proposal, solvent can be propene carbonate, ethylene carbonate, carbonic acid diethyl in the present inventionOne of ester, dimethyl carbonate, acetonitrile, water, N-Methyl pyrrolidone or several admixture solvents, but be not limited toThese types of solvent disclosed above, thus promote cushion gum layer additive, cushion gum layer lithium salts, cushion gum layer solid electrolyte itBetween be uniformly dispersed.The electrolytic polymer being scattered in core layer inorganic solid electrolyte can occur in extruder heating processCertain fusing, and then core layer inorganic solid electrolyte is adhesively fixed.
Then buffering adhesive and solid electrolyte rubber master batch are once squeezed out, squeeze out composite solid electrolyte piece again with anodeCompression molding of piece and negative electrode tab recycles liquid electrolyte confrontation lithium storage battery to carry out fluid injection, to effectively reduce lithium electric power storageInterface resistance inside pond, relative to by buffering adhesive, solid electrolyte rubber master batch in layer be coated on positive plate or negative electrode tabOn traditional operation, method of the invention effectively reduces the preparation step of lithium storage battery, effectively improves the production of lithium storage batteryEfficiency reduces its production cost to a certain extent.
Wherein, the liquid electrolyte in the present invention is preferably glyoxaline ion liquid, pyrrole ionic liquid and short chain rougeOne of fat ion liquid of quaternaries or a variety of mixtures, it is furthermore preferred that liquid electrolyte is 1- ethyl -3- methyl miaowAzoles fluoride salt (EMIF2.3HF), 1- butyl -3- methylimidazole hexafluorophosphate (BMIPF6), N- methyl butyl pyrrolidines two (threeMethyl fluoride sulphonyl) inferior amine salt (PyR14TFSI), two (trifluoromethyl sulphur of N, N- dimethyl-N-ethyl-N-2- methoxy ethyl ammoniumAcyl) inferior amine salt (DEMENTf2) one of or a variety of mixtures, but be not limited to these types disclosed above, dropped with thisInterface resistance between low positive plate, negative electrode tab and composite solid electrolyte piece.
In conclusion the invention has the following advantages:
1, lithium storage battery of the invention passes through positive plate, cushion gum layer, solid electrolyte core layer, cushion gum layer, negative electrode tabStructure setting, eliminates the setting of diaphragm, even if there is the foreign matters such as steel needle to pierce through or hit the solid electrolyte core layer and makeSolid electrolyte core layer ruptures, which inside it will rupture under the action of electrolytic polymerGap reduce or even restore, to keep original excellent partition effect so that lithium storage battery have good mechanical strength,Relatively high electric cycle performance and security performance.
2, lithium storage battery of the invention combines coextrusion technology and rolling techniques, and realization is processed and formed at one time, and reducesThe preparation step of lithium storage battery, effectively improves the production efficiency of lithium storage battery, reduces its production cost to a certain extent,It has the characteristics of easy operation.
Detailed description of the invention
Fig. 1 is the schematic diagram of internal structure for mixing solid-liquid electrolyte lithium battery；
Fig. 2 is the simple structure schematic diagram of the extrusion film-making of preparation mixing solid-liquid electrolyte lithium battery；
Fig. 3 is the test map of the capacity retention ratio of embodiment 1 and comparative example 1；
Fig. 4 is the test map of the capacity retention ratio of embodiment 1, comparative example 2 and comparative example 3.
In figure, 1, positive plate；11, positive electrode material layer；12, anode-supported layer；2, negative electrode tab；21, negative electrode material layer；22,Cathode-supported layer；3, composite solid electrolyte piece；31, solid electrolyte core layer；32, the first cushion gum layer；33, the second bufferingGlue-line.
Specific embodiment
Below in conjunction with attached drawing, invention is further described in detail.
It is a kind of mixing solid-liquid electrolyte lithium battery disclosed by the invention, including positive plate 1, negative electrode tab 2 referring to Fig. 1And it is set to the composite solid electrolyte piece 3 between positive plate 1 and negative electrode tab 2.Composite solid electrolyte piece 3 includes solid-state electricitySolution matter core layer 31 is set to solid electrolyte core layer 31 towards the first cushion gum layer 32 of 1 side of positive plate and is set toSecond cushion gum layer 33 of the solid electrolyte core layer 31 towards 2 side of negative electrode tab.
Wherein, positive plate 1 includes positive electrode material layer 11 and anode-supported layer 12 in the present invention.Positive electrode material layer 11 and firstCushion gum layer 32 is bonded, including positive electrode active materials, conductive agent, PEO, lithium salts and PVDF.Negative electrode tab 2 includes cathode in the present inventionMaterial layer 21 and cathode-supported layer 22.Negative electrode material layer 21 is bonded with the second cushion gum layer 33, and negative electrode material layer 21 includes cathodeActive material, conductive agent, paste agent and binder.
Solid electrolyte core layer 31 is mainly added by core layer inorganic solid electrolyte, electrolytic polymer and electrolyteAgent mixes, and the first cushion gum layer 32 and the second cushion gum layer 33 include cushion gum layer inorganic solid electrolyte, buffering adhesiveOne of layer lithium salts and buffering glue line additive or a variety of mixtures.
Preparation method of the invention is described in further detail below in conjunction with specific embodiment.
Embodiment 1
Referring to fig. 2, a kind of preparation method mixing solid-liquid electrolyte lithium battery, including following operating procedure:
1., the preparation of buffering adhesive
It is formulated for the buffering adhesive of molding the first cushion gum layer 32 and the second cushion gum layer 33, and the first cushion gum layer 32 and secondThe composition of cushion gum layer 33 is identical, specifically: 5g cushion gum layer lithium salts LiTFSI and 1g cushion gum layer is weighed by the weight ratio of 5:1The two is dissolved in 114g acetonitrile by additive PEO, is formed the organic polyelectrolyte glue that solid content is 5%, is added bufferingGlue-line inorganic solid electrolyte LLTO, mixing are dispersed into corresponding buffering adhesive, wherein the weight of cushion gum layer inorganic solid electrolyteAmount accounts for the 40% of the weight of corresponding electrolyte buffer glue respectively.
2., the preparation of solid electrolyte rubber master batch
By weight it is 80 by core layer inorganic solid electrolyte LLTO, electrolytic polymer PVDF, electrolyte additive DBP:10:10 is weighed, and core layer inorganic solid electrolyte LLTO first is carried out being mixed and made into masterbatch with electrolytic polymer PVDF,The electrolyte additive DBP of masterbatch and 3wt% are added twin-screw extrude again, heats and is kneaded through double screw extruderTo solid electrolyte rubber master batch.
3., the preparation of positive plate 1
3. -1, successively weighing positive electrode active materials, conductive agent carbon black, polyethylene glycol oxide, lithium salts by weight for 80:1:12:2:1LiTFSI and Kynoar, wherein positive active material is ternary material, spare.
3. -2, using N-Methyl pyrrolidone as solvent, by positive electrode active materials LiCoAnO2, conductive agent carbon black, PEO, lithiumSalt LiTFSI, PVDF are mixed with N-Methyl pyrrolidone, are stirred into the uniform anode sizing agent that solid content is 50%, are used forForm positive electrode material layer 11.
3. -3, by step, 3. -2 obtained anode sizing agents are coated on 12 aluminium foil of anode-supported layer of 10 μ m-thicks, through temperatureFor 120 DEG C, the speed of service be 1.0m/min drying, roll-in and after cutting, positive plate 1 is made.
4., the preparation of negative electrode tab 2
4. -1, by weight for 90:1:1:3 successively weigh negative electrode active material graphite, acetylene black, sodium carboxymethylcellulose andPVDF, it is spare.
4. -2, taking water as a solvent, negative electrode active material graphite, acetylene black, sodium carboxymethylcellulose and PVDF are mixedIt closes, stirs into the uniform negative electrode slurry that solid content is 60%, be used to form negative electrode material layer 21.
4. -3, by step, 4. -2 obtained negative electrode slurries are coated on 10 μm of 22 copper foil of cathode-supported layer, it is through temperature90 DEG C, after the speed of service is the drying of 1.0m/min, roll-in and cuts, negative electrode tab 2 is made.
5., it is coextruded profiled
1. buffering adhesive that step is prepared and 2. solid electrolyte rubber master batch that step is prepared are injected into extruder by the structure of settingAppointed part is once squeezed out by coextrusion techniques, in 80 DEG C of at a temperature of solvent evaporated, obtains composite solid electrolyte piece 3,By composite solid electrolyte piece 3, with step, 3. 4. negative electrode tab 2 obtained is sent into roll squeezer together for positive plate 1 obtained and step againIn, enough liquid electrolytes are injected in 90 DEG C of at a temperature of solvent evaporated by compression molding of hot pressing lamination processEMIF2.3HF carries out fluid injection process, and final mixing solid-liquid electrolyte lithium electric power storage is then made by existing battery preparation sectionPond, in mixing solid-liquid electrolyte lithium battery obtained, the first cushion gum layer (32), solid electrolyte core layer (31) and secondThe weight ratio of cushion gum layer (33) is 15:70:15, and thickness ratio is 20:60:20.
Embodiment 2
Difference from example 1 is that the present embodiment, in the preparation of buffering adhesive, cushion gum layer additive is PEO, only existCushion gum layer lithium salts is added in second cushion gum layer 33, which is LiTFSI, is weighed by the weight ratio of 5:105g cushion gum layer lithium salts LiTFSI and 10g cushion gum layer additive PEO is dissolved in acetonitrile, formed solid content be 10% it is organic poly-Polymer electrolyte glue；Cushion gum layer inorganic solid electrolyte is LAGP, and in the electrolyte buffer glue of formation, cushion gum layer is inorganic solidThe weight of state electrolyte accounts for the 60% of the weight of corresponding electrolyte buffer glue respectively.
In the preparation of solid electrolyte rubber master batch, core layer inorganic solid electrolyte is LAGP, and electrolytic polymer isPAA, electrolyte additive is stearic acid, and core layer inorganic solid electrolyte LAGP, electrolytic polymer PAA and electrolyte addAdding the stearic weight ratio of agent is 40:50:1.
In the preparation of positive plate 1, positive electrode active materials, conductive agent charcoal are successively weighed by weight for 90:5:5:10:5Black, polyethylene glycol oxide, lithium salts LiTFSI and Kynoar, positive active material are cobalt acid lithium, and temperature is 110 DEG C, operation speedDegree is 0.5m/min.
In the preparation of negative electrode tab 2, by weight for 95:3:2:2 successively weigh negative electrode active material graphite, acetylene black,Sodium carboxymethylcellulose and PVDF, negative electrode active material are Si-C composite material, and temperature is 130 DEG C, speed of service 20m/min。
The liquid electrolyte injected in fluid injection is BMIPF6.
In mixing solid-liquid electrolyte lithium battery obtained, the first cushion gum layer (32), solid electrolyte core layer (31)Weight ratio with the second cushion gum layer (33) is 5:85:10, and thickness ratio is 5:80:15.
Embodiment 3
Difference from example 1 is that the present embodiment, in the preparation of buffering adhesive, cushion gum layer additive is PEC, bufferingGlue-line lithium salts is LiBOB, weighs 10g cushion gum layer Lithium Salt LiBOB by the weight ratio of 1:1 and buffering glue line additive PEC is moltenYu Shuizhong forms the organic polyelectrolyte glue that solid content is 10%, and cushion gum layer inorganic solid electrolyte is LATP, is formedElectrolyte buffer glue in, the weight of cushion gum layer inorganic solid electrolyte accounts for the weight of corresponding electrolyte buffer glue respectively20%.
In the preparation of solid electrolyte rubber master batch, core layer inorganic solid electrolyte is that LATP and LLTO weight ratio is 1:1Mixture, electrolytic polymer PMMA, electrolyte additive is paraffin, and core layer inorganic solid electrolyte LATP, electricityThe weight ratio for solving matter polymer P MMA and electrolyte additive paraffin is 89:30:5.
In the preparation of positive plate 1, positive electrode active materials, conductive agent charcoal are successively weighed by weight for 85:5:10:5:2Black, polyethylene glycol oxide, lithium salts LiTFSI and Kynoar, positive active material are LiFePO4, and temperature is 150 DEG C, operationSpeed is 10.0m/min.
In the preparation of negative electrode tab 2, by weight for 90:2:2:3 successively weigh negative electrode active material graphite, acetylene black,Sodium carboxymethylcellulose and PVDF, negative electrode active material are lithium metal, and temperature is 100 DEG C, speed of service 0.5m/min.
The liquid electrolyte injected in fluid injection is PyR14TFSI。
In mixing solid-liquid electrolyte lithium battery obtained, the first cushion gum layer (32), solid electrolyte core layer (31)Weight ratio with the second cushion gum layer (33) is 70:25:5, and thickness ratio is 30:50:20.
Embodiment 4
Difference from example 1 is that the present embodiment, in the preparation of buffering adhesive, cushion gum layer additive is PTMC, delayRushing glue-line lithium salts is LiPF6, cushion gum layer inorganic solid electrolyte is Li2S-P2S5, in the electrolyte buffer glue of formation, bufferingThe weight of glue-line inorganic solid electrolyte accounts for the 20% of the weight of corresponding electrolyte buffer glue.
In the preparation of solid electrolyte rubber master batch, core layer inorganic solid electrolyte is Li3N；
The liquid electrolyte injected in fluid injection is DEMENTf2。
In mixing solid-liquid electrolyte lithium battery obtained, the first cushion gum layer (32), solid electrolyte core layer (31)Weight ratio with the second cushion gum layer (33) is 40:30:40, and thickness ratio is 30:40:30.
Embodiment 5
Difference from example 1 is that the present embodiment, in the preparation of buffering adhesive, cushion gum layer additive is PPC, bufferingGlue-line lithium salts is LiBF4, 15g cushion gum layer lithium salts LiBF is weighed by the weight ratio of 15:14It is molten with buffering glue line additive PPCYu Shuizhong, forms the organic polyelectrolyte glue that solid content is 12%, and cushion gum layer inorganic solid electrolyte is Li2S-SiS2,Electrolytic polymer is PVDF-HFP, electrolyte additive DOP；
In the preparation of solid electrolyte rubber master batch, core layer inorganic solid electrolyte is LLTO and Li3P(S0.5O0.5)4Weight ratioFor the mixture of 1:2.
In the preparation of positive plate 1, positive active material is lithium-rich manganese base material, and temperature is 130 DEG C, and the speed of service is10.0m/min。
In the preparation of negative electrode tab 2, negative electrode active material is nano silicon material, and temperature is 100 DEG C, and the speed of service is0.5m/min。
In mixing solid-liquid electrolyte lithium battery obtained, the first cushion gum layer (32), solid electrolyte core layer (31)Thickness ratio with the second cushion gum layer (33) is 10:85:5.
Embodiment 6
Difference from example 1 is that the present embodiment, in the preparation of buffering adhesive, cushion gum layer additive is VC, bufferingGlue-line lithium salts is LiCF3SO3, cushion gum layer inorganic solid electrolyte is Li3N；
In the preparation of solid electrolyte rubber master batch, core layer inorganic solid electrolyte is LiPON.
In the preparation of positive plate 1, positive active material is ternary material through solid electrolyte cladding or physical mixedComposite material, temperature are 120 DEG C, speed of service 10.0m/min；
Embodiment 7
Difference from example 1 is that in the present embodiment, the first cushion gum layer (32), solid electrolyte core layer (31)Thickness ratio with the second cushion gum layer (33) is 15:83:2.
Embodiment 8
Difference from example 1 is that the present embodiment, in the preparation of solid electrolyte rubber master batch, core layer inorganic solid-state is electricThe weight ratio for solving matter LLTO, electrolytic polymer PVDF and electrolyte additive DBP is 90:5:5.
Embodiment 9
Difference from example 1 is that the present embodiment is in the preparation of buffering adhesive, cushion gum layer lithium salts LiTFSI and bufferingGlue line additive PEO is that the ratio of 20:1 is dissolved in acetonitrile by weight.
Embodiment 10
Difference from example 1 is that the present embodiment is in the preparation of buffering adhesive, cushion gum layer inorganic solid electrolyteWeight accounts for the 10% of the weight of corresponding electrolyte buffer glue.
Embodiment 11
Difference from example 1 is that positive plate 1, negative electrode tab 2 and composite solid electrolyte piece 3 pass through in the present embodimentCorresponding lithium storage battery is made in traditional lamination process.
Embodiment 12
Difference from example 1 is that solid electrolyte rubber master batch first squeezes out solid electrolyte core is made in the present embodimentIt is slow to be correspondingly formed the first cushion gum layer 32 and second for layer 31, then the two sides by buffering adhesive coated on solid electrolyte core layer 31Composite electrolyte core layer 3 is made after rushing 33,80 DEG C of dry out solvent of glue-line, finally by composite electrolyte core layer 3 and positive plate 1Be sent into roll squeezer together with negative electrode tab 2, by compression molding of hot pressing lamination process, 90 DEG C at a temperature of be evaporated it is moltenCorresponding lithium storage battery is made in agent.
Comparative example 1
Difference from example 1 is that composite solid electrolyte piece 3 is without the first cushion gum layer 32 and the in this comparative exampleTwo cushion gum layers 33.
Comparative example 2
Difference from example 1 is that in this comparative example composite solid electrolyte piece 3 include solid electrolyte core layer31 and second cushion gum layer 33.
Comparative example 3
Difference from example 1 is that in this comparative example composite solid electrolyte piece 3 include solid electrolyte core layer31 and first cushion gum layer 32.
Comparative example 4
Difference from example 1 is that being not added with electrolytic polymer in the solid electrolyte core layer 31 of this comparative example.
Comparative example 5
Difference from example 1 is that it is not added with electrolytic polymer in the solid electrolyte core layer 31 of this comparative example,And PP membrane layer is additionally provided between solid electrolyte core layer 31 and the first cushion gum layer 32.
Comparative example 6
Comparative example 6 is that application No. is the lithium ion batteries of the Chinese invention patent disclosed embodiment 4 of 201611112927.X.
Lithium storage battery made from embodiment 1- embodiment 12 and comparative example 1- comparative example 6 is performed the following performance tests,Test result is referring to table one.
1, specific capacity plays the ratio test experiments for accounting for theoretical specific capacity: specific capacity of the invention plays as during productionThe specific reading of equipment shows that the summation including being normally melted into capacity and partial volume capacity is calculate by the following formula specific capacity performance and accounts forThe ratio of theoretical specific capacity: [(being normally melted into capacity+partial volume capacity)/theoretical specific capacity] × 100%.
2, cycle life performance test experiments: under constant current/constant voltage condition (60 DEG C of room temperature) of 1C/4.2V, eachBattery is counted by the charging of 1C/4.2V cut-off current and 1C/3.0V cut-off electric discharge when capacity retention ratio is 80% or moreCycle-index.
3, inner walkway is tested: internal resistance of the invention carries out AC impedance survey using Germany's Zahner electrochemical workstationExamination；Test macro is bis- electrode system of U-Buffer, and test frequency range is 0.01Hz-100KHz, amplitude 5mV.
4, it battery short circuit rate test experiments: is measured according to the standard of GB/T 31485-2015.
5, pricker percent of pass test experiments: being measured according to the standard of GB/T 31485-2015, probe diameter 5mm.
Table one
Interpretation of result
For embodiment 1 into embodiment 6, the specific capacity of lithium storage battery plays the ratio for accounting for theoretical specific capacity higher than 90.2%, recyclesService life is higher than 1210 times, and internal resistance is in 26.7-37.2m Ω, and battery short circuit rate is lower than 0.3%, and needle pierces percent of pass and is higher than 95.7%.It willEach performance synthesis gets up to account for, and the performance difference of the lithium storage battery of this six embodiments is little, all has excellent electricityCycle performance and security performance.For embodiment 7 into embodiment 12, the specific capacity of lithium storage battery plays the ratio for accounting for theoretical specific capacityFor 85.1-90.3%, cycle life is 1130-1279 times, and in 31.9-45.7m Ω, battery short circuit rate is 0.4-2.8% for internal resistance,It is 85.7-98.1% that needle, which pierces percent of pass,.Each performance synthesis is got up to account for, lithium electric power storage made from embodiment 1 to embodiment 6The comprehensive performance in pond is better than embodiment 7 to embodiment 12.
Wherein, first cushion gum layer is identical as the composition of the second cushion gum layer in embodiment 1, and first slow in embodiment 2It rushes in layer and eliminates cushion gum layer lithium salts, the component for not only having demonstrated two cushion gum layers can be the same or different, but also verifyingFirst cushion gum layer or the second cushion gum layer may include cushion gum layer inorganic solid electrolyte, cushion gum layer lithium salts, bufferingOne of glue line additive or a variety of mixtures.
Core layer inorganic solid electrolyte in embodiment 1 is LLTO, is the representative of oxidized form solid electrolyte, embodimentLAGP in 2 is the representative of vulcanization type solid electrolyte, the LATP and LLTO in embodiment 3 be sulfide type solid electrolyte withThe representative that oxide type solid electrolyte is used in mixed way, the Li in embodiment 43N is the representative of nitride type solid electrolyte, realApply the LLTO and Li in example 53P(S0.5O0.5)4It is used in mixed way for oxide type solid electrolyte and nitride type solid electrolyteIt represents.It is possible thereby to prove, core layer inorganic solid electrolyte can be oxide type solid electrolyte, sulfide type solid-state electricitySolve one of matter and nitride or a variety of mixtures.
Each defined in embodiment 1 to embodiment 4 and embodiment 7 first cushion gum layer, solid electrolyte core layer andThe thickness ratio of second cushion gum layer, can be obtained by its corresponding testing result, when the thickness ratio is (5-30): (40-90): (5-30)When, the performance of lithium storage battery obtained is better than not falling within performance of the thickness than interior lithium storage battery.
Core layer inorganic solid electrolyte, electrolytic polymer are defined in embodiment 1 to embodiment 4 and embodiment 8It with the weight ratio of electrolyte additive, can be obtained by its corresponding testing result, when the weight ratio is (40-89): (10-50): (1-10) when, the performance of lithium storage battery obtained is better than not falling within the performance of the lithium storage battery in the weight ratio.
The weight of cushion gum layer lithium salts Yu cushion gum layer additive is defined in embodiment 1 to embodiment 4 and embodiment 9Than, it can be obtained by its corresponding testing result, when the weight ratio is (5-15): when (1-10), the performance of lithium storage battery obtainedBetter than the performance for not falling within the lithium storage battery in the weight ratio.
Defined in embodiment 1 to embodiment 4 and embodiment 10 weight of cushion gum layer inorganic solid electrolyte with it is rightThe accounting for answering the weight of electrolyte buffer glue can be obtained by its corresponding testing result, when the weight accounting is 20%-60%,The performance of its lithium storage battery obtained is better than not falling within the performance of the lithium storage battery in the weight accounting.
Embodiment 1 and embodiment 11 and embodiment 12 each define the preparation method of lithium storage battery, by its corresponding detectionAs a result it can obtain, when preparing lithium storage battery using coextrusion technology and a molding method of pressure roller, lithium storage can be effectively improvedThe electric cycle performance and security performance of battery, while ensure that the excellent room-temperature conductivity of lithium storage battery.
Comparative example 1 on the basis of embodiment 1 respectively sets the first cushion gum layer and the second cushion gum layer to comparative example 3It sets and is made that adjustment, can be obtained by its corresponding testing result, although the pricker percent of pass of comparative example 2 is higher than 90%, had goodSecurity performance, but its specific capacity play account for theoretical specific capacity ratio and cycle life it is lower.In addition, applicant also extracts realityApply the measurement of the lithium storage battery progress capacity retention ratio of example 1 and comparative example 1- comparative example 3, specific testing result such as Fig. 3 and Fig. 4Shown, the capacity retention ratio of embodiment 1 is apparently higher than the capacity retention ratio of comparative example 1 and comparative example 2, and slightly above comparative example 3Capacity retention ratio.It is available in conjunction with the testing result of table one, the first cushion gum layer is set in lithium storage battery of the invention32 and second cushion gum layer 33 can be effectively improved the capacity retention ratio of lithium storage battery, and the first cushion gum layer 32 keeps capacitorThe influence of rate is significantly greater than the second cushion gum layer 33, thus, the first cushion gum layer 32 and the second cushion gum layer are arranged simultaneously33 can effectively improve the electric cyclicity of lithium storage battery.
Comparative example 4 and comparative example 5 on the basis of embodiment 1, are respectively made the component of solid electrolyte core layer 31Adjustment, can be obtained by its corresponding testing result, when in solid electrolyte core layer 31 for addition electrolytic polymer or by itsIt is substituted for PP membrane layer, the electric cycle performance and security performance of lithium storage battery obtained are decreased obviously.
Comparative example 6 is the septate lithium ion battery of existing band, by the testing result of its testing result and embodiment 1 intoRow compares, and available, electric cycle performance and differing for comparative example 6 of the invention is smaller, but needle pierces percent of pass and is substantially better than pairRatio 6, therefore the present invention has more excellent security performance.
To sum up, lithium storage battery produced by the present invention has excellent electric cycle performance and security performance, and preparation method is rawIt produces high-efficient, easy to operate.
This specific embodiment is only explanation of the invention, is not limitation of the present invention, those skilled in the artMember can according to need the modification that not creative contribution is made to the present embodiment after reading this specification, but as long as at thisAll by the protection of Patent Law in the scope of the claims of invention.